Carbohydrate derivative and process of making the same



Patented Oct. 8, 1935 I I UNITED STATES PATENT OFFICE CARBOHYDRATE DERIVATIVE AND' PROCESS OF MAKING THE SAM Ferdinand Schulze, Waynesboro, Va.., assignor to E. Ldu Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application January-9, 1934 Serial No. 705,898

9 Claims. (01. 260100) This invention relates to carbohydrate derivathe process of the present invention and that of tives, more particularly to cellulose derivatives, the prior art. Example III represents a prior art and even more particularly to cellulose derivatives process, Example IV the process of the present of sulfuric acid. invention.

United States Patent 1,734,291 to Gebauer- Example III 5- Fulnegg describes the preparation of cellulose sulfate by the use of chlorosulfonic acid on cellulose in the presence of pyridine. Traube in various patents discloses the direct addition of sulfur trioxide to cellulose and in British Patent 322,003 discloses the use of a diluent in carrying out the reaction.

This invention has as an object the preparation of carbohydrate derivatives of sulfuric acid of good quality, as indicated by the high viscosity of their solutions, by a method simple, effective and uncomplicated by the formation of colored Emample IV by-products difiicult of removal. A further 010- 543 parts by Weight of pyridine were mixed with ject is the preparation of sulfuric acid derivatives 160 parts by Weight f lf trioxide (2 mols of cellulose of similar high quality. Other objects d the mixture u Obtained heated with 50 20 Win appeathereinafterparts by weight of cotton linters pulp for about These ob ects are accomplished by the following one hour at The cotton swelled but no invention wherein sulfur trioxide is reacted With @0101- devehped, i tr st with the prior art cellulose in the presence of a tertiary amine such process f Example EL as pyridine. The reaction may take place at per- As starting material any of the ordinary Vari 25 haps and the profiuct be isolated by eties of cellulose may be used including wood dissolving the reaction mixture in water and copulp, cotton linters hydro or 0xy ce11u1ose and agulatil'lg the reaction Product by the addltlon partially substituted cellulose derivatives such as of alcohol. The following examples illustrates the low Substituted methyl ethyl or benzyl cellulose,

invention but are not limitalfive thereoflow substituted cellulose acetate, cellulose pro- 30 Example I pionate, glycol cellulose, and cellulose glycollic acid. Other polymeric carbohydrates or carbohy- One part by weight of ulfur trioxide is drate derivatives such as inulin, mannan, chitin,

tilled into ten parts by weight of pyridine and glyqogeni Starch may be used- A g many 35 about part by weight of cellulose in the form of tertlau"y ammes ma1y y the small strips of filter paper is added. The mixture examples @1115 the l s, coll dlnes, picolmes, is heated to 100 0. until the cellulose is dissolved Gwynne, dlethyl-p-tolwdene, u e. a d d1- 548 parts of pyridine were mixed with 232 parts by Weight (2 mols.) of chlorosulfonic acid and the mixture thus obtained heated with 50 parts by weight of cotton linters pulp at 100 C. for about 10 one hour. The cellulose swelled and a red color developed quite rapidly after a few minutes, the color becoming deeper until it was almost black. The color was removable only with difiiculty and long continued extraction or repeated reprecipitation.

and the product then isolated. methyl-p-xylidine are efiective. Pyridine-type tertiary ammes are, however, much more effective 40 Example II than other tertiary amines and for this reason represent a preferred embodiment of the inven- 17.1 parts by weight of sulfur trioxide are distion, tilled into 40 parts by weight of pyridine w The temperature of the reaction may be varied C ol 1? pa y weight of py are then from about 50 to about 150 C. although a temadded to get a pa ial S0111ti0n 0f the addition perature of about 100 C. to 120 C. is preferred. 45 Product 53 Parts by Weight o 00131301! linters P The reaction may be carried out under pressure are then added and the mixture heated to 90 C. nd th even higher temperatures may be emfor th ee d y The p p SWellS t y b does ployed. The time of reaction varies with the not dissolve. The reaction product is dissolved temperature and th desired degree of t in water, prec pitate by pouring into alcohol cation. In order to secure a water soluble prod- 50 while stirring, washed with ether to remove the uct, test samples may be taken and the reaction a o and dri d, fo xa p in a cator stopped when the desired solubility is obtained. over sulfuric acid. The product may be fibrous in the reaction mix- The following comparative experiments were ture or it may be in solution depending on the 55 carried out to illustrate the difierence between time and temperature of the reaction and the 55 ing swelling of the cellulose and which also have a solubilizing effect on the cellulose.

The cellulose sulfate obtained according to the process of the present invention is useful in general as the cellulose sulfate of the prior art but in addition is especially suitable for those purposes where the low viscosity or color contamination of prior art cellulose sulfates have, Thus, it may be.

rendered these undesirable. used as a dispersing agent, as a sizing material, or as an intermediate in the formation of other cellulose derivatives.

The present process is advantageous in affording a simple and efiective method of obtaining a cellulose sulfate of a low degree of degradation in a state susceptible of easy purification, differentiating in these two respects from theprocesses of the prior art.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except a defined in the appended claims.

I claim:

1. Process for the preparation of sulfuric acid derivatives of carbohydrates comprising reacting sulfur trioxide with a material containing a polymeric carbohydrate nucleus and free hydroxyl groups in the presence of a tertiary amine.

2. Process for the preparation of sulfuric acid of the pyridine type. 5

3. Process for the preparation of sulfuric acid derivatives of cellulose comprising reacting sulfur trioxide with a material-containing the cellulose' nucleus and free hydroxyl groups in the presence of a tertiary amine.

AeProcess for the preparation of sulfuric acid derivatives of cellulose comprising reacting sulfur trioxide with a material containing the cellulose nucleus and'free hydroxyl groups in the presence of a tertiary amine of the pyridine type.

5. Process for thepreparation of sulfuric acid derivatives of'cellulose comprising reacting sulfur trioxide with cellulose in the presence of a tertiary amine.

6. Process for the preparation of sulfuric acid derivatives of cellulose comprising reacting sulfur trioxide with cellulose in the presence of a tertiary amine of the pyridine type.

7. Process for the preparation of sulfuric acid derivatives of cellulose comprising reacting sulfur trioxide with cellulose at a temperature of 50 to 150 C. in the presence of a tertiary amine of the pyridine type. I

8. Process for the preparation of sulfuric acid derivatives of cellulose comprising reacting sulfur trioxide with cellulose at a temperature of 50 to 150 C. in the presence of pyridine.

9.. Process for the preparation of sulfuric acid esters of cellulose comprising reacting approximately 160 parts by weight of sulfur trioxide with approximately parts by weight of cellulose at a temperature of to C. in the presence of approximately 548 parts by weight of pyridine for approximately one hour.

' FERDINAND SCHULZE. 

